HK1213738A1

HK1213738A1 - Biocide composition comprising pyrithione and pyrrole derivatives

Info

Publication number: HK1213738A1
Application number: HK16101731.4A
Authority: HK
Inventors: ‧沃爾德隆; C‧沃尔德隆; ‧馬丁; R‧马丁; ‧威廉姆斯; G‧威廉姆斯
Original assignee: 阿奇化工公司
Priority date: 2006-03-03
Filing date: 2016-02-18
Publication date: 2016-07-15
Also published as: ES2636810T3; JP5956400B2; JP2009528356A; AU2007221987B2; AU2007221987B8; EP1998619B1; TWI394532B; EP1998619A2; WO2007103013A3; PL1998619T3; US20110144232A1; DK1998619T3; US20110104375A1; TW200803746A; US20070207178A1; WO2007103013A2; MY145917A; AU2007221987A1; US8481523B2; US8372829B2

Abstract

The present invention is directed to a biocidal composition comprising a blend of zinc pyrithione and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (traloypryil) wherein said biocidal composition is copper free or low copper content. A coating composition comprising this biocidal composition as well as a method of coating a substrate and a coated wood, plastic, leather vinyl or metal substrate are also disclosed.

Description

Biocidal composition comprising 2-mercaptopyridine-N-oxide and a pyrrole derivative

The application is a divisional application of Chinese patent application with application date of 2007 and 22 months and application number of 200780007736.X, and the invention name of the biocidal composition containing 2-mercaptopyridine-N-oxide and pyrrole derivatives.

Background

Technical Field

The present invention relates to a biocidal composition. More particularly, the present invention relates to a biocidal composition comprising a mixture of at least one selected 2-mercaptopyridine-N-oxide compound and at least one selected pyrrole derivative that prevents or inhibits the growth of microorganisms, and methods of using the biocidal composition.

Brief description of the Prior Art

Many compositions and formulations are known for preventing, inhibiting and treating microbial growth or spread. Likewise, a number of compositions and coatings are specifically formulated to prevent, inhibit and treat the growth or spread of fouling organisms.

Biofouling organisms pose significant problems for substrates and objects exposed to water. The term "biofouling organisms" includes both hard and soft biofouling organisms. Hard fouling organisms include barnacles, mollusks, and the like, while soft fouling organisms include algae, fungi, and organisms listed in U.S. Pat. No.5,712,275, which is incorporated herein by reference. Such organisms have been problematic for objects and substrates exposed to seawater, fresh water, salt water, tap water, waste water, rain water, and the like.

Fouling organisms grow, spread or adhere to various substrates and objects exposed to any type of water. The growth or spread of fouling organisms on the surface makes the appearance unattractive. In addition, growth can also cause problems with the use of substrates and objects that are contacted or spread by fouling organisms, for example, one of the frequently occurring problems is the contact of hard fouling organisms with the hull of a ship. Such organisms cause the surface of the ship to become rough, thereby reducing the speed of the ship.

In addition, wood and wood products often also have the growth and spread of microorganisms, such as biofouling organisms, termites, and the like. The growth and spread of such microorganisms causes the wood and wood products to become bent, cracked and deteriorated. Thereby losing value, aesthetic appeal, and usefulness of the wood and wood products.

To combat this problem, coatings containing biocides have been developed. Examples of useful biocides include tributyltin (tributylin) compounds, 2-mercaptopyridine-N-oxide compounds, and,Thiazine compounds, pyrrole compounds, triphenylboron compounds, and terbutyn.

The 2-mercaptopyridine-N-oxide compounds and the screened azole compounds are each known and are useful as biocides or anti-fouling agents. However, combining two compounds is not known or obvious in the art. Prior art documents teaching the use of 2-mercaptopyridine-N-oxide compounds and screened azole compounds include, for example, the following:

U.S. Pat. No.5,057,153 to Ruggiero relates to an improved paint or paint base characterized by enhanced biocidal efficacy. The coating contains a biocide comprising a salt of 2-mercaptopyridine-N-oxide and a copper salt. In addition, U.S. Pat. No.5,246,489 to Farmer Jr et al discloses a method for generating 2-mercaptopyridine-N-oxide copper salt biocides in situ in a binder. The coatings and binders of this patent comprise a 2-mercaptopyridine-N-oxide compound which acts as the sole biocide in the formulation.

U.S. Pat. No.5,098,473 to Hani et al relates to coatings and binders and more particularly to a method of providing stable, gel-free dispersions of zinc 2-mercaptopyridine-N-oxide salts and cuprous oxide biocides in coatings (see also U.S. Pat. Nos. 5,098,473; 5,112,397; 5,137,569; 5,185,033; 5,232,493; 5,298,061; 5,342,437; PCT patent application Nos. WO 95/10568 and EP 0610251).

French et al, U.S. patent No.4,957,658, relates to coatings and binders, and more particularly to a method and composition for providing coatings and binders having reduced discoloration containing 2-mercaptopyridine-N-oxide and iron ions.

U.S. patent No.4,399,130 to Davidson et al describes a method of treating or preventing porcine exudate dermatitis using an effective amount of at least one pyridine-2-thione-N-oxide metal salt.

U.S. Pat. No.4,496,559 to Henderson et al describes selective derivatives of 2-selenopyridine-N-oxides for use as fungicides and bactericides.

U.S. Pat. No.4,565,856 to Trotz et al relates to polymers containing 2-mercaptopyridine-N-oxide. The polymers described in this patent are useful as biocides in coatings and wood preservative products.

U.S. patent No.4,610,993 to Wedy et al describes a method of administering an effective amount of at least one selected pyridine-N-oxide disulfide to treat or prevent bovine mastitis.

European patent EP 0746979 describes a method for controlling or combating the contact of fouling organisms with underwater surfaces by contacting the organisms with an anti-fouling-effective amount of a 2-arylpyrrole compound.

U.S. patent No.6,069,189 to Kramer et al describes anti-fouling coatings containing selected azole derivatives. Specific azole compounds for incorporation in the anti-fouling coating include 2-trihalomethyl-3-halo-4-cyanopyrroles and derivatives thereof. Kramer et al found these compounds to be particularly effective in combating the spread of barnacles. Furthermore, the Kramer et al reference found that bright or light colored anti-fouling coatings could be obtained despite the addition of these compounds.

PCT patent application No. wo 03/039256 describes an anti-fouling composition comprising at least 3.5 wt% of 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, or a salt thereof, and another biocide, based on the total weight of dry matter of the composition. The other biocide is selected from the group consisting of pyridoxal, tolylfluanid, dichlofluanid, and DCOIT.

Despite the advances made in the art, there remains a need for coatings comprising biocidal compositions that are effective against a wide range of microorganisms and that exhibit high durability and low toxicity. In theory, the coatings and compositions should be easy and inexpensive to produce. The present invention is believed to be the answer to the above-mentioned problems.

Brief description of the invention

Accordingly, one aspect of the present invention relates to a biocidal composition comprising one or more 2-mercaptopyridine-N-oxide compounds and one or more pyrrole compounds of formula I:

wherein X is halogen, CN, NO₂Or S (O)_nR₁(ii) a Y is hydrogen, halogen or S (O)_nR₁(ii) a Z is halogen, C₁-C₄Haloalkyl or S (O)_nR₁(ii) a n is an integer 0,1 or 2; r₁Is C₁-C₄A haloalkyl group; l is hydrogen or halogen; m and Q are each independently hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy radical, C₁-C₄Alkylthio radical, C₁-C₄Alkylsulfinyl radical, C₁-C₄Alkylsulfonyl, CN, NO₂、R₂CO or NR₃R₄Or when M and Q are in adjacent positions and are linked together at the linking carbon atom, MQ represents the structure-OCH₂O-、-OCF₂O-or-CH-; r is hydrogen, C₁-C₄Alkoxyalkyl group, C₁-C₄Alkylthioalkyl or R₆CO；R₂Is C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy or NR₃R₄；R₃Is hydrogen or C₁-C₄An alkyl group; r₄Is hydrogen, C₁-C₄Alkyl or R₅CO；R₅Is hydrogen or C₁-C₄An alkyl group; and R₆Is C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy radical, C₂-C₆Alkenyloxy radical, C₁-C₄Haloalkoxy, optionally substituted by 1-3C₁-C₄Alkyl-substituted phenyl, benzyl, phenoxy, benzyloxy, C₁-C₄Alkyl carbonyl oxy, C₃-C₆Cycloalkyl, naphthyl, pyridyl, thienyl or furyl, wherein the biocidal composition is copper-free or has a low copper content.

As defined herein, the term halogen refers to Cl, Br, I or F, and the term haloalkyl refers to any alkyl C having from 1 halogen atom to 2n +1 halogen atoms_nH_2n+1Wherein the halogen atoms are the same or different.

Another aspect of the invention relates to a coating composition comprising an effective amount of a biocidal composition comprising one or more 2-mercaptopyridine-N-oxide compounds and one or more pyrrole compounds of formula (I) above, wherein the biocidal composition is copper-free or has a low copper content.

Yet another aspect of the invention relates to a method of coating a substrate comprising applying a coating composition comprising a biocidal composition to the substrate and drying the coating composition on the substrate, wherein the coating composition comprises one or more 2-mercaptopyridine-N-oxide compounds and one or more pyrrole compounds of formula (I) above.

Yet another aspect of the invention relates to a coated substrate comprising the coating composition and a substrate, wherein the coating composition contains the biocidal composition of the present invention, wherein the substrate is selected from the group consisting of wood, plastic, leather, vinyl, and metal.

One expected advantage of the present invention includes improved protection against a wide range of microorganisms. Another contemplated advantage of the present invention includes the preservation of wood and wood products. In addition, the compositions of the present invention are expected to be long lasting, low in toxicity and easy and inexpensive to prepare.

Detailed Description

The term "biocidally effective amount" as used in the description and claims of the present invention relates to an amount of a biocidal composition that has a positive effect on reducing, eliminating or preventing contact or growth of microorganisms on a substrate.

The term "microorganism" as used in the specification and claims of the present invention includes algae, fungi, biofilms, insects, fouling organisms (including hard and soft fouling organisms), or any organism capable of contacting, growing on or destroying materials such as wood, concrete, paper, plastics and the like.

The term "copper free or having a low copper content" as used in the description and claims of the present invention means that the composition does not contain copper or that the total weight percent copper contained is less than 3 wt% based on the total weight of the formulation.

The term "wood product" as used in the specification and claims of the present invention includes materials containing or derived from wood, including but not limited to particle board, chip board, plywood, wood flake fiberboard, laminated wood, pressed wood, and the like.

As indicated above, one aspect of the present invention is a biocidal composition comprising one or more 2-mercaptopyridine-N-oxide compounds and one or more pyrrole compounds according to formula (I) above. Each of these components will be discussed in detail below.

In general, 2-mercaptopyridine-N-oxides are widely known and are commonly used in many applications, including coatings and personal care products. 2-mercaptopyridine-N-oxide is an excellent biocide and is found in antifouling marine paints. In addition, metal salts of 2-mercaptopyridine-N-oxide, including tin, cadmium and zirconium salts, are also suitable for use in shampoos.

Preferably, the 2-mercaptopyridine-N-oxide in the biocidal composition has the following basic structure:

the 2-mercaptopyridine-N-oxide compounds suitable for use in the present invention include zinc 2-mercaptopyridine-N-oxide salts, copper salts,Sodium, pyridine-N-oxide disulfide,A disulfide, 2' -dithio-pyridine-1, 1-dioxide, or pyridine-2-thione-N-oxide. The 2-mercaptopyridine-N-oxide compounds have excellent biocidal effects. 2-mercaptopyridine-N-oxide zinc and copper salts have low solubility in brineAnd thus they are more durable than other 2-mercaptopyridine-N-oxide salts, so zinc and copper salts of 2-mercaptopyridine-N-oxide are most preferred.

The zinc and copper salt compounds of 2-mercaptopyridine-N-oxide may be prepared according to the method described in U.S. Pat. No.2,809,971 to Berstein et al. Other patents disclosing similar compounds and methods for their preparation include U.S. patent nos. 2,786,847; no.3,589,999; and No.3,773,770.

Furthermore, the biocidal compositions of the present invention comprise one or more pyrrole compounds of formula (I) as shown above. Preferably, the pyrrole compound is a 2-trihalomethyl-3-halo-4-cyanopyrrole derivative substituted in the 5-position and optionally in the 1-position, the halogens in the 2 and 3 positions are independently selected from fluorine, chlorine and bromine, and the substituent in the 5-position is selected from the group consisting of: c_1-8Alkyl radical, C_1-8Monohaloalkyl, C_5-6Cycloalkyl radical, C_5-6Monohalocycloalkyl, benzyl, phenyl, mono-and di-halobenzyl, mono-and dihalophenyl, mono-and di-C_1-4Alkylbenzyl, mono-and di-C_1-4Alkylphenyl, monohalogenated mono-C_1-4-alkylbenzyl and monohalogenated mono-C_1-4-alkylphenyl, any halogen in the substituent in position 5 being selected from chlorine and bromine, optionally the substituent in position 1 being selected from C_1-4Alkyl and C_1-4Alkoxy radical C_1-4An alkyl group. Among the 2-arylpyrrole compounds suitable for use in the methods and compositions of the present invention are: 4, 5-dichloro-2- (α, α, α -trifluoro-p-tolyl) pyrrole-3-carbonitrile; 4-bromo-5-chloro-2- (p-chlorophenyl) pyrrole-3-carbonitrile; 4-bromo-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 3, 4-dichloro-2- (3, 4-dichlorophenyl) pyrrole-5-carbonitrile; 4-chloro-2- (p-chlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 4, 5-dibromo-2- (p-chlorophenyl) -3- (trifluoromethylsulfonyl) pyrrole; 4-bromo-2- (3, 5-dichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 2- (p-chlorophenyl) -5- (trifluoromethyl) -4- (trifluoromethylthio) pyrrole-3-carbonitrile; 4-bromo-2- (2,3, 4-trichlorophenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 4-bromo-2- (2,3, 5-trichlorophenyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile; 4-bromo-2- (p-chlorophenyl) -5- (α, α, β, β -tetrafluoroethylthio) pyrrole-3-carbonitrile; 4-bromo-2- (m-fluoro)Phenyl) -5- (trifluoromethyl) pyrrole-3-carbonitrile; 2- (3, 5-dichlorophenyl) -5- (trifluoromethyl) -4- (trifluoromethylthio) pyrrole-3-carbonitrile; and 4-bromo-2- (p-chlorophenyl) -5- [ (β -bromo- β, α, α -trifluoro) -ethylthio]Pyrrole-3-carbonitrile. Most preferably, formula (I) is 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile.

The compounds of formula (I) described above may be prepared according to the methods described in U.S. Pat. Nos. 5,310,938 and 5,328,928.

To ensure the effectiveness of the biocide, the weight ratio of the 2-mercaptopyridine-N-oxide compound to the compound of formula (I) in the biocidal composition is preferably from 9:1 to 1: 9. More preferably, the weight ratio of the 2-mercaptopyridine-N-oxide compound to the compound of formula (I) in the biocidal composition is from 3:2 to 2: 3. Most preferably, the weight ratio of the 2-mercaptopyridine-N-oxide compound to the compound of formula (I) in the biocidal composition is from 3:1 to 1: 3.

Another aspect of the present invention includes a coating composition comprising the above biocidal composition. The biocidal composition is present in the coating composition in a biocidally effective amount. The biocidally effective amount is from 1% to 15% by weight based on the total weight of the coating composition. Preferably, the biocidal composition is present in an amount of 1% to 15% by weight, based on the total weight of the coating composition. More preferably, the biocidal composition is present in an amount of 1% to 10% by weight, based on the total weight of the coating composition. Most preferably, the biocidal composition is present in an amount of 3% to 8% by weight, based on the total weight of the coating composition.

In addition to the biocidal composition, the coating composition may also include additives. Such additives may include, but are not limited to, organic binders; a processing aid; fixatives, such as polyvinyl alcohol; a plasticizer; a UV stabilizer; a dye; a color pigment; an anti-settling agent; an anti-foaming agent; additional pesticides such as chlorinated hydrocarbons, organophosphates, and the like; additional fungicides and bactericides, such as alcohols, aldehydes, formaldehyde-releasing compounds, and the like; phenol; organic acids such as propionic acid, benzoic acid, and the like; inorganic acids such as boric acid; an amide; an azole; a heterocyclic compound; n-haloalkylthio compounds; and so on. Self-polishing polymers, such as acrylic polymers or acrylic copolymers, may also be used, for example, in marine anti-fouling coatings. Preferably, these polymers do not contain tin. Examples of acrylic polymers and copolymers that may be additionally used in the composition of the present invention include copper acrylate polymers or copolymers, zinc acrylate polymers or copolymers, silyl acrylate polymers or copolymers, and the like. Other polymers known in the coatings and coatings art may also be used in the compositions of the present invention. The additives present in the coating composition will depend on the preference of the user or manufacturer and the end use of the coating composition.

The coating composition is formed by incorporating the biocidal composition and the additive into a binder material, such as a marine binder. Methods of forming such coating compositions are well known in the art. Examples of such methods include, but are not limited to, combining biocidal compositions and additives in a mixing device. The mixing device uniformly disperses the biocidal composition in the additive. Other methods of forming the coating composition may be used in a manner known to those skilled in the art. In addition, any binder material suitable for marine applications, including water or solvent-based formulations, may be used in the compositions of the present invention. As described, for example, in U.S. patent nos. 6,710,117; 4,981,946, respectively; 4,426,464, respectively; 4,407,997 and 4,021,392, such marine coatings are known in the art.

The coating composition may take various forms. Those forms include, but are not limited to, coatings, (especially anti-fouling coatings), varnishes, lacquers (lacquers), detergents, wood sealants, or any form that can be used to coat materials.

Another aspect of the present invention includes a method comprising applying the above-described coating composition to a material intended to be protected. The coating composition may be applied in a variety of ways, including but not limited to brushing, spraying, wiping, spraying, or dipping, immersing, or soaking the material therein. The coating composition is preferably applied to the material in a uniform form. Once the coating composition is applied to the material, it should be allowed to dry to ensure that it adheres properly to the material. Drying may be achieved by exposure to air, or by using a device that can dry faster, such as a heat lamp or hot air generator.

Materials that may be protected by the coating composition include wood, leather, vinyl, plastic, concrete, paper, and any other material that may be exposed to microorganisms or water containing such microorganisms. Ideally, the material should be sufficiently porous to allow the coating composition to penetrate and adhere to the material.

Another aspect of the invention includes a coated substrate. The coated substrate comprises the above-described material coated with a coating composition. Substrates that may greatly benefit from the application of the coating composition include conventional marine substrates such as boat hulls, docks, piers, buoys, fishing tools, fishing nets, lobster traps, bridges and pile structures. However, the substrate to which the coating composition is applied may also include concrete, wallboard, decking, siding, or any other substrate that is in constant or frequent contact with water or microorganisms.

It is expected that the substrate will exhibit biocidal properties when coated with the coating composition. This biocidal property will prevent, inhibit or treat contact or growth of microorganisms on or within the substrate. Prevention and treatment of such growth will protect the substrate from microbial attack. In addition to making the appearance of the substrate attractive, protection from microbial attack may also allow the substrate to be used in the intended manner.

Further, it is expected that wood and wood products coated with the coating composition will exhibit microbial resistance. It is expected that the coating composition will prevent microorganisms, such as fungi, algae, termites, etc., from destroying the appearance appeal and utility of wood and wood products after application to the wood and wood products. Commercial and residential products and buildings, including stairways, floors, cabinets, decks, piers, signs, stakes, fences, furniture, mailboxes, and the like, would also benefit from this application.

Examples

The following examples further illustrate the invention. All parts and percentages are by weight unless explicitly stated otherwise. All temperatures are degrees celsius unless explicitly stated otherwise.

Paint efficacy test

In 2004, the university of duck near the bank of the boverth sea, north carolina, tested a series of 9 paint formulations containing 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-Pyrrole-3-carbonitrile (referred to as Pyrrole in the table below) and zinc 2-mercaptopyridine-N-oxide salt (ZPT) for their anti-fouling effect on barnacles and other fouling organisms. Formulations were made in the laboratory by adding varying amounts of biocide to the resin-based formulations (vinyl resin/wood rosin and zinc oxide filler). The formulations include 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile alone or in combination with ZPT. A solvent-based zinc oxide coating was used as a control. Unprimed glass fiber rods (8mm diameter x 11cm length) were dip-coated with each formulation (5 rods/formulation) and suspended from the test rack into the ocean (1 meter below the sea surface). Each month, barnacles and bryozoans were evaluated for each stick. The most desirable results are obtained from the formulation of 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile in combination with ZPT (see table 1 below).

Bryozoa are highly complex groups of animals constructed from a single "zoospore", in which all zoospores are joined by living tissue. Zoospores are protected within a cup-or box-shaped, calcified shell tissue exoskeleton. The degree of calcification controls the degree of stiffness and softness of the entire structure. Many herbivores feed on bryozoans, such as sea urchins and various mollusks.

This study demonstrates that 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile is an effective anti-fouling agent for hard fouling organisms, such as barnacles, which is compatible with ZPT, and which works better with ZPT as a co-biocide than it works alone.

TABLE 1

Note that "M" refers to the mature foulant population. The life cycle of certain marine organisms can lead to differences in the average number/month seen in the above table.

While the invention has been described with reference to the above specific embodiments thereof, it is apparent that many changes, modifications, and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications and variations that fall within the spirit and broad scope of the appended claims.

Claims

1. A biocidal composition comprising:

a.) one or more 2-mercaptopyridine-N-oxide compounds, and

b.) one or more pyrrole compounds of formula (I):

wherein X is halogen, CN, NO₂Or S (O)_nR₁(ii) a Y is hydrogen,Halogen or S (O)_nR₁(ii) a Z is halogen, C₁-C₄Haloalkyl or S (O)_nR₁(ii) a n is an integer 0,1 or 2; r₁Is C₁-C₄A haloalkyl group; l is hydrogen or halogen; m and Q are each independently hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy radical, C₁-C₄Alkylthio radical, C₁-C₄Alkylsulfinyl radical, C₁-C₄Alkylsulfonyl, CN, NO₂、R₂CO or NR₃R₄Or when M and Q are in adjacent positions and are linked together at the linking carbon atom, MQ represents the structure-OCH₂O-、-OCF₂O-or-CH-; r is hydrogen, C₁-C₄Alkoxyalkyl group, C₁-C₄Alkylthioalkyl or R₆CO；R₂Is C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy or NR₃R₄；R₃Is hydrogen or C₁-C₄An alkyl group; r₄Is hydrogen, C₁-C₄Alkyl or R₅CO；R₅Is hydrogen or C₁-C₄An alkyl group; and R₆Is C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy radical, C₂-C₆Alkenyloxy radical, C₁-C₄Haloalkoxy, optionally substituted by 1-3C₁-C₄Alkyl-substituted phenyl, benzyl, phenoxy, benzyloxy, C₁-C₄Alkyl carbonyl oxy, C₃-C₆Cycloalkyl, naphthyl, pyridyl, thienyl or furyl; and is

Wherein the biocidal composition is copper-free or has a low copper content.

2. The biocidal composition of claim 1 wherein said 2-mercaptopyridine-N-oxide compound is a non-copper metal salt of 2-mercaptopyridine-N-oxide.

3. The biocidal composition of claim 2 wherein said non-copper metal salt of 2-mercaptopyridine-N-oxide is selected from the group consisting of zinc 2-mercaptopyridine-N-oxide salt and iron 2-mercaptopyridine-N-oxide salt.

4. The biocidal composition of claim 3 wherein said non-heavy metal salt of 2-mercaptopyridine-N-oxide is a zinc salt of 2-mercaptopyridine-N-oxide.

5. The biocidal composition of claim 1 wherein said azole compound of formula (I) is selected from the group consisting of: a 2-trihalomethyl-3-halo-4-cyanopyrrole derivative substituted in the 5-position and optionally in the 1-position, the halogens in the 2 and 3 positions being independently selected from the group consisting of fluorine, chlorine and bromine, the substituent in the 5-position being selected from the group consisting of: c_1-8Alkyl radical, C_1-8Monohaloalkyl, C_5-6Cycloalkyl radical, C_5-6Monohalocycloalkyl, benzyl, phenyl, mono-and di-halobenzyl, mono-and dihalophenyl, mono-and di-C_1-4Alkylbenzyl, mono-and di-C_1-4Alkylphenyl, monohalogenated mono-C_1-4-alkylbenzyl and monohalogenated mono-C_1-4-alkylphenyl, any halogen in the substituent in position 5 being selected from chlorine and bromine, optionally the substituent in position 1 being selected from C_1-4Alkyl and C_1-4Alkoxy radical C_1-4An alkyl group.

6. The biocidal composition of claim 5 wherein the pyrrole compound is a 2-trihalomethyl-3-halo-4-cyanopyrrole.

7. The biocidal composition of claim 1 wherein the weight ratio of 2-mercaptopyridine-N-oxide compound to said compound of formula I is from 9:1 to 1: 9.

8. The biocidal composition of claim 1 wherein the weight ratio of 2-mercaptopyridine-N-oxide compound to said pyrrole compound of formula I is from 3:2 to 2: 3.

9. The biocidal composition of claim 1 wherein the weight ratio of 2-mercaptopyridine-N-oxide compound to said pyrrole compound of formula I is from 3:1 to 1: 3.

10. The biocidal composition of claim 1 further comprising at least one acrylic acid polymer or copolymer selected from the group consisting of: copper acrylate polymers or copolymers, zinc acrylate polymers or copolymers, silyl acrylate polymers or copolymers, and combinations thereof.

11. A coating composition comprising a biocidally effective amount of a biocidal composition comprising:

A) one or more 2-mercaptopyridine-N-oxide compounds; and

B) one or more pyrrole compounds of formula (I):

wherein X is halogen, CN, NO₂Or S (O)_nR₁(ii) a Y is hydrogen, halogen or S (O)_nR₁(ii) a Z is halogen, C₁-C₄Haloalkyl or S (O)_nR₁(ii) a n is an integer 0,1 or 2; r₁Is C₁-C₄A haloalkyl group; l is hydrogen or halogen; m and Q are each independently hydrogen, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy radical, C₁-C₄Alkylthio radical, C₁-C₄Alkylsulfinyl radical, C₁-C₄Alkylsulfonyl, CN, NO₂、R₂CO or NR₃R₄Or when M and Q are in adjacent positions and are linked together at the linking carbon atom, MQ represents the structure-OCH₂O-、-OCF₂O-or-CH-; r is hydrogen, C₁-C₄Alkoxyalkyl group, C₁-C₄Alkylthioalkyl or R₆CO；R₂Is C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy or NR₃R₄；R₃Is hydrogen or C₁-C₄An alkyl group; r₄Is hydrogen, C₁-C₄Alkyl or R₅CO；R₅Is hydrogen or C₁-C₄An alkyl group; and R₆Is C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy radical, C₂-C₆Alkenyloxy radical, C₁-C₄Haloalkoxy, optionally substituted by 1-3C₁-C₄Alkyl-substituted phenyl, benzyl, phenoxy, benzyloxy, C₁-C₄Alkyl carbonyl oxy, C₃-C₆Cycloalkyl, naphthyl, pyridyl, thienyl or furyl; and is

Wherein the biocidal composition is copper-free or has a low copper content.

12. The coating composition of claim 11 wherein said 2-mercaptopyridine-N-oxide compound is a non-copper metal salt of 2-mercaptopyridine-N-oxide.

13. The coating composition of claim 12, wherein said non-copper metal salt of 2-mercaptopyridine-N-oxide is selected from the group consisting of a copper salt of 2-mercaptopyridine-N-oxide and a zinc salt of 2-mercaptopyridine-N-oxide.

14. The coating composition of claim 13, wherein the metal salt of 2-mercaptopyridine-N-oxide is a zinc salt of 2-mercaptopyridine-N-oxide.

15. The coating composition of claim 11, wherein the pyrrole compound of formula (I) is a 2-trihalomethyl-3-halo-4-cyanopyrrole.

16. The coating composition of claim 11, wherein the biocidally effective amount is 1% to 15% by weight based on the total weight of the coating composition.

17. The coating composition of claim 16, wherein the biocidally effective amount is 2% to 10% by weight based on the total weight of the coating composition.

18. The coating composition of claim 17, wherein the biocidally effective amount is 3% to 8% by weight based on the total weight of the coating composition.

19. The coating composition of claim 11, wherein the weight ratio of 2-mercaptopyridine-N-oxide compound to said compound of formula I is from 9:1 to 1: 9.

20. The coating composition of claim 11, wherein the weight ratio of 2-mercaptopyridine-N-oxide compound to the pyrrole compound of formula I is from 3:2 to 2: 3.

21. The coating composition of claim 11, wherein the weight ratio of 2-mercaptopyridine-N-oxide compound to the pyrrole compound of formula I is from 3:1 to 1: 3.

22. The coating composition of claim 11, wherein the coating composition is a coating.

23. The coating composition of claim 11, wherein the coating composition is a varnish.

24. The coating composition of claim 11, wherein the coating composition is a paint.

25. The coating composition of claim 11, wherein the coating composition is a wood sealant.

26. The coating composition of claim 11, further comprising at least one acrylic polymer or copolymer selected from the group consisting of: copper acrylate polymers or copolymers, zinc acrylate polymers or copolymers, silyl acrylate polymers or copolymers, and combinations thereof.

27. A method of coating a substrate, the method comprising:

applying the coating composition of claim 11 to a substrate; and

drying the coating composition on the substrate.

28. The method of claim 27, wherein the substrate is selected from the group consisting of wood, plastic, leather, vinyl, and metal.

29. The method of claim 27, wherein the substrate is exposed to water.

30. A coated substrate, the coated substrate comprising:

the coating composition of claim 11; and

a substrate, wherein the substrate is a glass substrate,

wherein the substrate is selected from the group consisting of wood, plastic, leather, vinyl, and metal.

31. A coating composition, comprising:

a biocidal composition comprising from about 2 to about 4 weight percent of a zinc 2-mercaptopyridine-N-oxide salt compound, based on the total weight of the coating composition, and from about 2 to about 5 weight percent of 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, based on the total weight of the coating composition; the biocidal composition is substantially free of copper or has a low copper content; and

a marine paint base;

wherein said zinc 2-mercaptopyridine-N-oxide salt and said 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile are present in said coating composition in a weight ratio of from about 2.5:1 to about 1: 2.